DE3632847A1 - METHOD FOR PRODUCING VANADINE PENTOXIDE - Google Patents

Description

The invention relates to the Ge offers chemistry and metallurgy, in particular Process for the preparation of vanadium pentoxide which is used for Manufacture of vanadium compounds, additional alloys and catalysts are widely used.

The vanadium-containing slags obtained in the smelters were in the processing of titanium magnetite ores, their Vanadium content of 0.5 to 2% as the main raw material for the production of vanadium pent oxide. (Here and in the following all data in% by weight.)

In the USSR a flow diagram of the complex ver development of the titanium magnetite ores developed and large technically recorded that the simultaneous Ausbrin iron and vanadium from these on pyrometallur path. According to the analogous scheme Titanium magnetite ores in the Republic of South Africa and China processed (K. M. Sokolova "Proizvodstvo i potreblenie vanadia za rubezhom ", bulletin of the institute" Cher metinformatsia ", 1981, Issue 10, 1894, pp. 3-15).

According to this scheme, titanium magnetite ores processed into vanadium pig iron, which continues through Oxidation with a gaseous oxidizing agent in Kon is processed into steel and vanadium slag.

The obtained vanadium slag serves as a raw material for the production of vanadium pentoxide.

The process for the production of vanadium pentoxide Converter slag provides the following operations: Preparation of the slag for roasting (crushing, Grinding, divorce, mixing with a reaction medium), oxidizing roasting, leaching of the roasted Möllers in a solvent (with water, acid solution and alkalis), cases of pentavalent vanadium the solutions, drying, melting and granulation of the obtained vanadium pentoxide.

Other processes for the production of vanadium pentoxide from roscoelite, carnotite, patronite ores and com complex ores, from bauxites and phosphorites  basically the main stages of this scheme.

The simplest variant of the hydrometallurgical Process for the application of vanadium from Titanomagne titen was realized in Finland (N.P. Lyakishev et al. "Vanadium in iron metallurgy" (Vanadii v chernoi metal lurgii), Moscow, Metallurgizdat, 1983, p. 192). A ge low silicon and calcium content in the starting ore Oxides make it possible to concentrate iron vanadium obtained, which contains: 67-67.7% Fe, 0.58% SiO₂, 2.8% TiO₂, 0.98-1.12% V₂O₅, 0.2% CaO. For this concentrate Vanadium is applied without reducing the level of application to carry out enrichment by pyrometallurgical means. The essence of this technology is that oxydie roasting of rolling balls containing soda (2%) is carried out and then won sodium vanadate NEN, from which according to the known operations (Fall oil, washing, drying, smelting) containing 95% or more vanadium pentoxide; the degree the application of vanadium is 77.5%. This However, the procedure is due to the agreement of the used composition of the raw material with requirement technology unique.

In most cases, titanium magnetites stand out due to higher concentrations of calcium oxide and pebble earth out and for this reason is the technology mentioned not suitable for their processing.

In this case there is a manufacturing process of vanadium pentoxide from a vanadium converter slag has been developed in processing the one set slag containing vanadium for roasting, roasting the same in the presence of a reaction supplement, leaching of the roasted mill and the separation of the preserved ones Vanadium solution from the cake, precipitation of vanadium pentoxide as well Drying and melting take place. (N.P. Lyaki shev u. a. "Vanadium in iron metallurgy (Vanadii v chernoi metallurgii) ", Moscow, Metallurgizdat, 1983, p. 31).

This brings 65-85% vanadium into the aqueous solution out. In addition to the vanadium, however, aluminates, titanates and  Silicates that form the water glass, which under separation of a colloidal precipitate is hydrolyzed in solution. As a result, the filtration of the pulp is deteriorated and the finished vanadium pentoxide through silicon, aluminum oxides and other elements contaminated. The end product preferably contains 80-85% and in the best cases 87-88.0% vanadium pentoxide.

This procedure requires it to achieve a high level Degree of application of vanadium for the production of Vanadium pentoxide several main parameters at the optimal Operational management to meet the raw materials and characterize the process on the whole.

The vanadium slag should be based on its chemical, mineralo the chemical composition and grain composition the porosity, strength, density and. a. at the on preparation for roasting (phase separation, comminution), when roasting (reducing the ability to sinter), when stopping lye (increase in the yield of vanadium as well as Improved filterability of the pulp) high characteristic ensure values. That is why the choice is used composition of the miller and the vanadium slag of great importance.

The object of the present invention was Production of vanadium pentoxide from a Möller, which makes it possible to check the purity of the vanadinhalti solutions and the quality of the end product to improve.

This task is carried out in a process for Production of vanadium pentoxide, in the treatment Riding the Möller by mixing the vanadium slag and soda, roasting the furniture in an oxidizing Atmosphere, leaching of the roasted furniture, separation the vanadium solution obtained from the cake and precipitation from Vanadium pentoxide is obtained from the solution mentioned, solved according to the invention by the Möller by mixing of 10-40% soda and 60-90% vanadium slag following Composition, in%

Calcium oxide 3-40 Magnesium oxide 2-15 Vanadium oxide14-30 Silicon oxide12-32 Oxides of iron, titanium,
Chromium, manganese, aluminum, phosphor residue

with a weight ratio of SiO₂: (CaO + MgO) the same 0.75-0.85, is processed.

A preferred variant of the method mentioned is a process in which in the Möller with Vanadium slag and soda cake in a lot from 3 to 15% obtained in the leaching stage of the roasted miller is introduced.

The present invention allows the Ausbrin from vanadium from Möller to the finished product Increase 1-2%, the filtration speed of the water solutions containing vanadium to ver 5-10 times enlarge.

A detailed description of the Procedure cited.

One uses for the production of vanadium pentoxide Vanadium slag that comes from the wind freshening of vanadium raw iron with an oxidizing agent in oxygen converters using magnesium and / or calcium containing Fabrics can be won as a surcharge.

The vanadium slag should have the following composition, in % By weight, have:

Calcium oxide 3-40 Magnesium oxide 2-15 Vanadium oxide14-30 Silicon oxide12-32 Oxides of iron, titanium,
Chromium, manganese, aluminum, phosphor residue

The oxides mentioned are chosen within the limits mentioned so that the weight ratio SiO₂: (CaO + MgO) in Möller 0.75-0.85.  

The stated ratio of silicon dioxide to the sum the oxides of calcium and magnesium begin in the Möller the formation of thermodynamically stronger and more stable Silicates that make it possible in the watery Leaching the roasted Möllers solutions with a ge lower content of silicon, manganese and to get other elements. It also makes it possible mentioned ratio SiO₂: (CaO + MgO), which for the be known process characterized high turbidity intensity education that reduces the spreading of vanadium, belittling.

The vanadium slag of the composition mentioned crushed and mixed with calcined soda following ratio of the components, in% by weight:

Soda10-40 Vanadium slag 60-90

The ratios of the components of the oil mentioned lers, d. H. the vanadium slag and soda are that with a reduction in soda content in Möller by less than 10 wt .-% of the application rate of vanadium from roasted Möller in solution 60% not exceeds what an additional stage of application, for example, requires acidic leaching, which is the end product by admixtures, for example with manganese and phosphorus, significantly contaminated.

An increase in the soda content of the miller to over 40% is impractical, since it does not application of vanadium and the quality of the End product not improved and in some cases un desired sintering of the Möllers and the Reduces roasting productivity.

The vanadium oxide content of the vanadium slag gives from the fact that when the salary is reduced of vanadium oxide to below 14% of reagent consumption 1 t of finished product is significantly increased, and for one Vanadium oxide content of over 30% of the spread of vanadium by increasing the intensity of the sintering is reduced by the Möller when it is roasted.  

The Möller of the composition mentioned is at roasted at a temperature of 700 to 800 ° C. The roasted one Möller z. B. with water at a temperature of Leached 70 to 90 ° C and the pulp obtained is from filtered. The filtration goes with a large one Speed ahead.

A high filtration rate of the pulp after leaching the furniture is obtained, as well as the required degree of purity after filtration of the Pulp solution obtained is only in the aforementioned Zu composition of the vanadium slag in which the Oxide content in% as follows: 3-40 calcium oxide, 2-15 magnesium oxide, 14-30 vanadium oxide, 12-32 silicon oxide, Rest: oxides of iron, titanium, chromium, manganese, aluminum, Phosphorus.

After filtering the pulp, the cake is obtained and solutions containing vanadium. To make Vana The vanadinhal can use high purity dinpentoxide solutions for the time being with aluminum salts, for example wise with aluminum chloride, aluminum sulfate or with Alum are treated. Vanadium is made from the solutions in Form of ammonium vanadate precipitated. The won Precipitation from ammonium vanadate is filtered, washed dry, in an oxidizing atmosphere glows and then at a temperature of 670 to 720 ° C melted. The result is vanadium pentoxide.

To reduce the loss of vanadium with cake (Heap) and consequently to increase the total yield gens of vanadium from the slags are led into the Moller containing vanadium slag and soda 3-15% Cake one that is in the stage of leaching the toasted Möllers is won and the 1-3% vanadium pent contains oxide.

The stated additional amount of cake results from the fact that a cake additive in an amount of less than 3% on the increase in vanadium application does not affect and that a cake additive in a Amount of more than 15% the performance of roasting the oil  lers reduced and contaminated the end product.

The inventive method for the production of Vanadium pentoxide has compared to the known The following advantages:

• - The spreading of vanadium from the Möller into the Final product is enlarged;
• - the filtration rate of the vanadinhalti gene pulp is from 1-5 m³ solution / m²St to 25-35 m³ / m²St enlarged;
• - the content of admixtures in vanadium-containing Solutions as well as in the end product will be 1.5-2 times reduced;
• - The cost per 1 t of finished vanadium pentoxide is reduced.

A preferred embodiment of the Invention cited.

You prepare the Möller by mixing 25-30% soda ash and 70-75% vanadium slag, which contains in%:

Calcium oxide 9-15 Magnesium oxide 4-6 Silicon oxide 12-15 Vanadium oxide 14-20 Oxides of Fe, Mn, Ti, Cr, Al, PRest

The mass ratio of silicon dioxide to the sum the oxides of Ca and Mg such as SiO₂: (CaO + MgO) in the Vana din slag is in a range from 0.75 to 0.85. The prepared Möller is in the air at a tempe roasted from 740 to 760 ° C. Leach the roasted one Möller with water at a solid-liquid ratio of the components solid: liquid = 1: (2-4) and one temperature between 70 and 80 ° C. The ge recovered pulp is used to separate the solid residue of the cake containing 1-3% vanadium pentoxide filtered. The solution obtained, the 25-65 g / l vanadium Contains pentoxide, treated at a temperature from 80 to 95 ° C with ammonium salts, for example Am  monium sulfate, at a pH of 2.0 to 2.5, which one when cutting by introducing an inorganic acid, for example, sulfuric acid. The resulting one Precipitation of ammonium vanadate is filtered off and washed with water, dries at a temperature of 100 to 150 ° C, glows in the oxidizing atmosphere at Temperature of 250 to 450 ° C and melts at a two between 670 and 720 ° C. The finished (melted) vanadium pentoxide contains in%: V₂O₅-95.3, V₂O₄-1,2, remainder of Fe, Si, Mn, S, P, Cr. The application of V₂O₅ in water Solution makes up 91-94%.

In order to produce vanadium pentoxide high Degrees of purity (over 98.0%) are introduced into the filtered off Solution containing 25-65 g / l V₂O₅, in addition to the ammo nium salts aluminum salts, for example aluminum alum, a. Silicon and other additives are deposited beaten and the precipitate is filtered off. The filtered solution is added an inorganic salt and at a pH of 2.0 to 2.5, ammonium falls vanadate, which you glow and get a final product, that contains in%: V₂O₅-99.8, V₂O₄-0.1, remainder of Fe, Si, Mn, S, P, Cr.

To better understand the present Er Examples are given below, which the Illustrate preparation of vanadium pentoxide.

Example 1

You make a Möller by mixing 10% calcined soda and 90% vanadium slag, which contains in%:

Calcium oxide 3 Magnesium oxide15 Silicon oxide15 Vanadium oxide 28 Oxides of Fe, Ti, Cr, Mn, Al, PRest

The weight ratio is in the vanadium slag of SiO₂: (CaO + MgO) equal to 0.85.  

The manufactured Möller is exposed to air at a tem roasted at 700 ° C. The roasted Möller will with water at the solid-liquid ratio of the phases like Solid: liquid = 1: 4 and leached at 75 ° C. The receive The pulp is filtered off. The solid precipitation (Cake) contains 3% vanadium pentoxide.

The filtered solution contains 64 g / l vanadium pent oxide mixed with ammonium sulfate at a pH of 2.0-2.2 is precipitated in the form of ammonium vanadate. The precipitate of ammonium vanadate is filtered off, washes, dries at a temperature of 140 to 150 ° C, glows at a temperature of 300 to 450 ° C and melts at a temperature between 680 and 720 ° C temperature.

The final product (melted product) contains in %: V₂O₅-94.0, V₂O₄-1.0, remainder of Fe, Si, Cr, Mn, S, P.

Example 2

You make a Möller by mixing 20% calcined soda and 80% vanadium slag, which contains in%:

Calcium oxide 11 Magnesium oxide 5 Silicon oxide 12 Vanadium Oxide 30 Oxides of Fe, Ti, Cr, Mn, Al, PRest

The weight ratio is in the vanadium slag of SiO₂: (CaO + MgO) equal to 0.75. The manufactured Möller is in air at a temperature of 700 ° C roasts. The roasted Möller is mixed with water at one Solid-liquid ratio of the phases like solid: liquid = 1: 4 and leached out at a temperature of 80 ° C. The pulp obtained is filtered off. The won Solution contains 69 g / l vanadium pentoxide and the cake contains 3% vanadium pentoxide. The vanadium pentoxide in the Solution is precipitated with ammonium sulfate at a pH  from 2.4 to 2.5 in the form of ammonium vanadate. Man filters the precipitate of ammonium vanadate, washes, dries at a temperature of 140 to 150 ° C, glows at a temperature of 320 to 440 ° C and melts at a temperature between 680 and 720 ° C.

The final product (melted product), the Vana Dinpentoxide, contains in%: V₂O₅-94.5, V₂O₄-0.9, Remainder of Fe, Si, Mn, Cr, S, P.

Example 3

You make a Möller by mixing 40% calcined soda and 60% vanadium slag, which contains in%:

Calcium oxide40 Magnesium oxide 2 Silicon oxide32 Vanadium Oxide 14 Oxides of Fe, Ti, Cr, Mn, Al, PRest

The weight ratio is in the vanadium slag of SiO₂: (CaO + MgO) equal to 0.75. The Möller is at roasted at a temperature of 800 ° C. The roasted Möller with water at a solid-liquid ratio leached from 1: 4 and a temperature of 90 ° C. The pulp obtained is filtered off. The solid residue (the cake) contains 1% vanadium pentoxide.

The filtered solution contains 32.5 g / l vanadium pentoxide, which one with ammonium sulfate at a pH from 1.9 to 2.1 in the form of ammonium vanadate.

The precipitate of ammonium vanadate is filtered from, washes, dries at a temperature of 150 ° C, glows at a temperature of 380 to 430 ° C and melts at a temperature between 680 and 720 ° C temperature.

The molten end product, vanadium pentoxide, ent holds in%: V₂O₅-95.1, V₂O₄-0.4, rest of Fe, Si, Mn, Cr, S, P.  

Example 4

You make a Möller by mixing 25% soda ash and 75% vanadium slag, which contains in%:

Calcium oxide15 Magnesium oxide 5 Silicon oxide 16 Vanadium Oxide 25 Oxides of Fe, Ti, Cr, Mn, Al, PRest

The weight ratio is in the vanadium slag of SiO₂: (Ca + MgO) equal to 0.80.

The Möller is ge at a temperature of 750 ° C roasts. The roasted Möller is mixed with water at one Solid-liquid ratio of 1: 3 and at one temperature leached from 80 ° C. The pulp obtained is filtered from. The solid residue (the cake) contains 2.1% vana dinpentoxide and the filtered solution contains 32.5 g / l V₂O₅. The vanadium pentoxide coincides with the solution Ammonium sulfate at a pH of 2.0 to 2.2.

After repeating the same operations as in Examples 1-3 are described, the end product contains in %: V₂O₅-94.8, V₂O₄-0.8, remainder of Fe, Si, Mn, Cr, S, P.

Example 5

A Möller described in Example 2 is added 3% cake, obtained with water leaching, added. Other operations and parameters of roasting Möller, the filtration and precipitation as well as other labor gears are similar to those described in Example 2 Lich.

The finished vanadium pentoxide contains in%:
V₂O₅-94.4, V₂O₄-0.9, remainder of Fe, Si, Mn, Cr, S, P.

Example 6

A Möller described in Example 3 is added 15% cake, obtained with water leaching,  added. Other operations and parameters of roasting Möller, the filtration and precipitation as well as other labor gears are similar to those described in Example 3 Lich.

The finished vanadium pentoxide contains in%:
V₂O₅-95.0, V₂O₄-0.4, remainder of Fe, Si, Mn, Cr, S, P.

Example 7

 A Möller described in Example 4 is added 8% cake, obtained with water leaching, added. Other operations and parameters of roasting von Möller, filtration and precipitation as well as others Operations are those described in Example 4 similar.

The finished vanadium pentoxide contains in%:
V₂O₅-94.9, V₂O₄-0.7, remainder of Fe, Si, Mn, Cr, S, P.

Claims (2)

1. Process for the preparation of vanadium pentoxide, with preparation of the furniture by mixing vanilla slag and soda, roasting it in an oxidizing atmosphere, leaching out the roasted furniture, separating the vanadium solution obtained from the cake and precipitating the vanadium pentoxide from the solution, characterized that the Möller by mixing 10-40% soda and 60-90% vanadium slag of the following composition, in wt .-%: calcium oxide 3-40 magnesium oxide 2-15 vanadium oxide 14-30 silicon oxide 12-32 oxides of Fe, Cr, Mn, Ti, Al, PRest processed with a weight ratio of silicon dioxide to the sum of calcium and magnesium oxides in the slag equal to 0.75-0.85 (all data in percent by weight). 2. The method according to claim 1, characterized ge indicates that the Möller 3-15% cake contains that in the stage of leaching the ge roasted Möllers is obtained.